Food Anal.

Methods (2014) 7:352359

DOI 10.1007/s12161-013-9633-5

Application of Dispersive LiquidLiquid Micro-extraction

Using Mean Centering of Ratio Spectra Method for Trace
Determination of Mercury in Food and Environmental Samples
Mohadese Hossien-poor-Zaryabi & Mahmoud Chamsaz &
Tahereh Heidari & Mohammad Hossein Arbab Zavar &
Mohammad Behbahani & Mani Salarian

Received: 5 December 2012 / Accepted: 23 April 2013 / Published online: 4 May 2013
# Springer Science+Business Media New York 2013

Abstract In the present study, dispersive liquidliquid

micro-extraction has been applied for trace extraction and
determination of mercury (Hg) ions in environmental samples. The mean centering of ratio spectra method was
used to optimize the experimental parameters affecting
the extraction of Hg. The factors influencing the extraction procedure such as type and volume of extracting
and disperser solvent, concentration of chelating reagent,
pH, salt effect, and centrifuge time were investigated
and optimized. Under the optimized conditions, the limit
of detection of the method was 0.15 g l1 and enrichment factor was 39. The calibration curve was linear in
the range of 0.5100 g l 1 with a correlation of
determination (R2) of 0.998. The relative standard deviation for determination of 40 g l1 of Hg(II) was
2.6 % (n=5). The proposed method was applied for
the determination of Hg in pine leaf, sea and river fish,
sand, and water samples as indicators of environmental
pollution and cigarette with satisfactory analytical results. In comparison with other methods, the proposed
method is very simple, easy, rapid, and sensitive for
determination of Hg at trace levels in complex matrices.
M. Hossien-poor-Zaryabi (*) : M. Chamsaz : T. Heidari :
M. H. A. Zavar
Department of Chemistry, Faculty of Sciences,
Ferdowsi University of Mashhad, Mashhad, Iran
e-mail: m.hosseinpoorzaryabi@gmail.com
M. Behbahani : M. Salarian
Department of Chemistry, Faculty of Sciences,
Shahid Beheshti University, Tehran, Iran

Keywords Mercury . Dispersive liquidliquid microextraction . Mean centering of ratio spectra method .
Bioindicator

Introduction
Mercury (Hg) can be taken into the body through food or
breathing air. Hg can also be absorbed through the skin, at a
lesser extent. Exposure to Hg can cause tremors, memory
loss, damage to the brain and kidneys, and changes in
personality, vision, and hearing (Argonne National
Laboratory 2005). Hg is a naturally occurring metal as a
result of the normal breakdown of minerals in rocks and
soils from exposure to wind and water and from volcanic
activity. The major source of Hg pollution is waste incinerators and coal-fired utilities (Roundhill 2004). Some sophisticated instrumental techniques are extensively used as
standard methods in the determination of Hg, but they still
possess some disadvantages, such as high cost of instruments, matrix interference, and is time consuming. Spectrophotometry has been most commonly used for quantitative
analysis of Hg in solution due to the relatively inexpensive
instrumentation and simple operation procedure although its
biggest drawback is the low sensitivity which can only
detect Hg at parts per million (in milligrams per liter) level
normally. However, Hg usually exists in the environment at
parts per billion (in micrograms per liter) level with complicated matrix, so extraction and preconcentration procedures
are often indispensable (Tuzen and Soylak 2005; Tuzen et
al. 2009a, b, c, d).

Food Anal. Methods (2014) 7:352359

So far, a number of techniques have been used for the

pretreatment of Hg species from water samples. Although
traditional liquidliquid extraction (Gaona and Valiente
2003) was still employed, new methods such as singledrop micro-extraction (SDME) (Pena-Pereira et al. 2009),
liquidliquidliquid micro-extraction (Xia et al. 2007),
solid-phase extraction (Hashempur et al. 2008) for this
purpose have recently been developed. Owing to the low
level of trace analytes in samples, these pretreatment approaches play an important role in Hg speciation.
Recently, Assadi et al. (Rezaee et al. 2006) developed a
new micro-extraction technique termed dispersive liquid
liquid micro-extraction (DLLME), in which a solvent system containing a mixture of water-immiscible extraction
solvent and water-miscible disperser solvent is injected rapidly by a syringe into an aqueous sample. After extraction,
the cloudy solution is centrifuged and the enriched analytes
in the sediment phase are determined by chromatographic or
spectrometric methods (Yousefi and Shemirani 2010; Cheng
and Dong 2005; Dadfarnia and Haji Shabani 2010;
Bernardo et al. 2010; Yamini and Faraji 2010; Gharehbaghi
and Shemirani 2011; Tabrizi 2010; Liang and Sang 2008;
Wen et al. 2011; Kocorova et al. 2010; Zhoua et al. 2011).
Spectrophotometric methods are very simple, fast, and
inexpensive but lack selectivity and sensitivity. In spectrophotometry, the reagent blank response usually is subtracted
from the standard response, when the product and one of the
reagents absorb at the same wavelength and hence, the blank
absorbance at the end of reaction can be lower than that
measured in the beginning as a result of reagent consumption. Therefore, the real absorbance of the product will be
larger than the measured value. More recently, a new approach (Afkhami et al. 2007; Afkhami and Bahram 2005;
Afkhami and Bahram 2004; Afkhami and Bahram 2006;
Afkhami et al. 2005) has been proposed for simultaneous
analysis of binary and ternary mixtures called mean centering
of ratio spectra. This method uses mathematical equations to
give correct responses which can be used for determining
analyte concentration which is free from bias and error. This
method eliminates derivative steps and therefore signal-tonoise ratio is greatly enhanced (Chamsaz et al. 2010).
The aim of this work was to combine DLLME with
ultravioletvisible (UVvis) spectrometry to develop an
improved procedure for the determination of Hg traces in
pine leaf, sea and river fish, cigarette, and water samples
with respect to the advantages of DLLME which is a fast
and inexpensive method in comparison with other methods
of determining Hg. Furthermore, low consumption of organic solvents (at microliter levels) is another advantage of
this method, and finally, the authors have gained a good
limit of detection (LOD) with a simple instrument like UV
vis spectrophotometer compared with other sophisticated
instruments (Gao and Ma 2011). In this work, dithizone

353

was used as a suitable chelating agent to form complex with

Hg and factors that would influence the efficiency of
DLLME were also investigated and eventually, mean centering of ratio spectra method was used to eliminate blank
bias error.

Experimental
Reagents
All of the reagents used were of analytical grade and purchased from Merck (Darmstadt, Germany). Metal salts,
dithizone (1,5-diphenylthiocarbazone), and used extraction
and disperser solvents were of analytical grade, and all were
purchased from Merck (Darmstadt, Germany). Deionized
water was used for all dilutions. Stock metal solution of
1,000 mg l1 of Hg(II) was prepared by dissolving appropriate amounts of mercuric chloride in 1 % H2SO4. Standard
solutions of Hg were prepared daily by appropriate dilution
of stock solutions. Dithizone was used without further purification. The reagent solution was prepared daily by dissolving 0.5 mg of dithizone in 10 ml of ethanol.
Instrumentation
Phase separation by centrifugation was used by Centurion
Scientific Centrifuge (Model Andreas HettichD72,
Tuttlingen, Germany). The pH values were measured with
a pH meter (Metrohm, 632) supplied with a glass-combined
electrode. A 1.0-ml syringe (Saddle Brook, NJ, USA) was
used to inject the mixture of extraction and disperser solvents into the sample solution. A sampler (Eppendorf, Hamburg, Germany) was used to inject the sediment phase into
the quartz cell. All spectrophotometric measurements were
made with an Agilent 8453 spectrophotometer equipped
with a 1-cm path length glass cell. The spectrophotometer
was interfaced to a personal computer furnished with the
G1115A software.
Mean Centering of Ratio Spectra
Consider a mixture of two compounds X and Y. If there is no
interaction among the compounds and Beers law is obeyed
for each compound, it can be written (20):
Am aX CX aY CY

Where Am is the vector of the absorbance of the mixture,

X and Y the molar absorptivity vectors of X and Y, and CX
and CY are the concentrations of X and Y, respectively. If
Eq. (1) is divided by Y corresponding to the spectrum of a
standard solution of Y in binary mixture, the first ratio

354

Food Anal. Methods (2014) 7:352359

spectrum is obtained in the form of Eq. (2) (for possibility of

dividing operation, the zero values of Y should not be used
in the divisor):
B Am =aY aX CX =aY CY

If Eq. (2) is mean centered since the mean centering of a

constant (CY) is zero, Eq. (3) would be obtained:
MCB MC aX CX =aY

The minimum or maximum of these vectors with respect

to wavelength is used for the construction of the calibration
graph for analyte.
Dispersive LiquidLiquid Micro-extraction Procedure
One milliliter of 40 g l1 Hg solution at pH of 1.8 was
added into a 15-ml test tube with conical bottom. One
milliliter of 1.2105 mol l1 solution of dithizone as a
chelating agent was added to the solution, and the solution
was diluted to 10 ml with deionized water. Then, a mixture
of solution containing 750 l of ethanol (as disperser solvent) and 70 l of chloroform (as extraction solvent) was
rapidly injected into the sample solution using a 2-ml glass
syringe. A stable cloudy solution (water, ethanol, and chloroform) appeared, and the mixture was centrifuged for 1 min
at 4,000 rpm. The sedimented phase at the bottom of the test
tube was separated and diluted with 60 l of acetone and
transferred into a 250-l cell and its absorbance was measured at 495 nm with UVvis spectrophotometer. The stored
sample spectra were divided by the spectrum of the blank
solution according to Eq. (2), and mean centering of these
vectors with respect to the wavelength was obtained
according to Eq. (3). The minimum or maximum of these
vectors with respect to wavelength is used for the construction of the calibration graph for Hg.

H2SO4 was added to the solution and further evaporated until

evaluation of white smog to remove HNO3. The solution was
filtered through an ashless WhatmanR filter paper (40 ashless ).
Finally, the Hg(II) in the cigarette sample was determined by
the proposed analytical method (Fan et al. 2008).
Sea and River Fish
Two fish samples were obtained from the Caspian Sea and
Sefidrood River, Iran. Each sample was placed in a watch
glass, rinsed with water, and dried in an oven at 150 C. Five
grams of dried fish muscle was digested with 6 ml of
concentrated HNO3 (65 %) and 2 ml of concentrated H2O2
(30 %) and heated for 10 h. The proteins were precipitated
and separated during the digestion process. The resulted
solution was filtered through an ashless WhatmanR filter
paper for remove the precipitated proteins (40 ashless)
(Tuzen et al. 2009a, b, c, d; Nabid et al. 2012).
Sand Samples
Two sand samples were obtained from the Caspian Sea and
River Sefidrood, Iran. Each sample were placed in a watch
glass, rinsed with water, and dried in an oven at 50 C. One
gram of dried sand samples were dissolved in 20 ml of a
mixture of 12 mol l1 HCl, 14 mol l1 HNO3, and 18 mol l1
H2SO4 and heated for 12 h. The solution was filtered
through an ashless WhatmanR filter paper (40 ashless).
Pine Leaf
One gram of pine leaf was dissolved in 25 ml of 18 mol l1
HNO3 and heated for 24 h, and then it was filtrated and
evaporated to about 1 ml. Finally, the Hg(II) in the pine leaf
sample was determined by the proposed analytical method.

Results and Discussion

Real-Sample Pretreatment for Hg Analysis
Water Samples
Water samples including sea water (Caspian Sea), river
water (River Sefidrood), and well water were collected from
north of Iran. All the above real-water samples were filtered
through an ashless WhatmanR filter paper (40 ashless).
Cigarette
For Hg analysis of cigarette, first, the filter tip of tobacco
was removed and 1 g of the sample was dissolved in 25 ml
of 18 mol l1 HNO3 and heated for 24 h, then it was filtered
and evaporated to about 4 ml. After that 5 ml of 18 mol l1

As the absorbance spectra of Hg(II)-dithizone complex

and dithizone overlap, mean centering of ratio spectra
was applied for accurate determination of Hg(II)dithizone complex. Due to the overlapping of the sample and blank spectra, the blank signal was subtracted
from the sample signal. By applying mean centering of
ratio spectra (Yousefi and Shemirani 2010; Cheng and
Dong 2005; Dadfarnia and Haji Shabani 2010; Bernardo
et al. 2010; Yamini and Faraji 2010), the blank signal
was eliminated thoroughly and the sample signal was
obtained accurately. The effects of different parameters
such as pH, type, and volume of the extraction and
disperser solvents, centrifuge time, and potential interferences were studied.

Food Anal. Methods (2014) 7:352359

Effect of pH
The pH of the sample solution is a very important factor
which affects the complex formation of Hg with dithizone.
The effect of pH on the Hg complex extraction from water
samples was studied in the range of 113.5. The results are
given in Fig. 1, and as the results show, the optimum pH for
extraction of Hg is 1.8. In respect to the complex reaction
balance, in pH values lower than 1.8, severe acid effect and
the instability of Hg(HL)2 occur, while high pH values
probably cause the hydrolysis of Hg2+ and subsequent decomposition of Hg(HL)2 which finally decreases the absorbance signal, therefore, pH of 1.8 was selected as the
optimum pH for further experiments.
Mechanism for the complexation between Hg(II) and
dithizone is:
Hg2 2 H2 DZUHgHDZ2 2H H2 DZ is dithizone acidic medium
alkaline medium
Hg2 H2 DZ 2OH UHgDZ 2 H2 O

Selection of Extracting Solvent

355

than water, increased extracting capability together with low

solubility in water and showed higher mean centering of ratio
spectra.
Selection of Disperser Solvent
Miscibility of the disperser solvent with extracting solvent
and the sample solution is the most important criteria for
selection of disperser solvent. Thereby, acetone
((CH 3 ) 2 CO), acetonitrile (CH 3 CN), dimethyl ether
(CH3OCH3), isopropyl alcohol ((CH3)2CHOH), methanol
(CH3OH) and ethanol (C2H5OH) were tested as candidates
of disperser solvents. The Hg complex was extracted using
0.5 ml of each disperser solvent containing 100 l of chloroform. The results are shown in Fig. 2. According to the
obtained results, ethanol was selected as the best disperser
solvent for efficient extraction of Hg(II)-dithizone. Ethanol
was soluble in chloroform and was miscible in water.Ethanol
enabled to disperse chloroform as fine particles in the aqueous
phase and to form a cloudy solution (water/ethanol/chloroform)
showing higher mean centering of ratio spectra.

The type of extracting solvent used in DLLME is of great

importance for efficient extraction. In most cases, the ideal
extraction solvent has two properties, one is hydrophobicity,
and the other one is to have higher solubility for the analytes
compared with water. Chloroform (CHCl3), carbon tetrachloride (CCl4), dicloromethane (CH2Cl2), ethyl acetate
(C4H8O2), chlorobenzene (C6H5Cl), and benzyl alcohol
(C6H5CH2OH) were studied as extracting solvents. The Hg
complex was extracted using 0.5 ml of acetone (disperser
solvent) containing 100 l of each extracting solvents.
According to the obtained results, chloroform was selected
as the best extracting solvent. Chloroform had higher density

In order to obtain the optimum volume of extracting

solvent, solutions containing different volumes of chloroform (50, 70, 100, 125, and 150 l) and 0.5 ml of
ethanol were used in DLLME procedure. By increasing
of the extraction solvent volume, the final organic phase
obtained by centrifugation is increased, resulting in a
decrease of the concentration of the target analyte in
organic phase. Although the extraction recovery remains
almost constant, the enrichment factor will be decreased,
leading to a decrease of the sensitivity of the

Fig. 1 The effect of pH on absorbance of 40 g/l Hg (II). Conditions:

100 l chloroform, 0.5 ml ethanol, 1.2105 mol l1 of dithizone as a
chelating agent, and 2 min centrifugation time

Fig. 2 The effect of type of disperser solvent on absorbance of 40 g/l

Hg (II). Conditions: 100 l chloroform, 0.5 ml disperser solvent,
pH 1.8, 1.2105 mol l1 of dithizone as a chelating agent, and
2 min centrifugation time

Optimization of Extracting Solvent Volume

356

determination for the target ions. As the results, the

maximum absorbance was obtained using 70 l of the
extracting solvent.
Optimization of Disperser Solvent Volume
The disperser solvent volume directly affects the formation
of the cloudy solution (water/disperser solvent/extraction
solvent), the degree of the dispersion of the extraction
solvent in aqueous phase, and the extraction efficiency. In
order to examine the effect of disperser solvent volume,
solutions containing different volumes of ethanol (0.25,
0.5, 0.75, and 1 ml) and 70 l volume of extracting solvent
were used in DLLME procedure. The results given in Fig. 3
illustrate that 0.75 ml of disperser solvent was chosen as the
optimum disperser solvent volume.
Effect of Centrifuge Time
The effect of centrifuge time on the extraction efficiency
was tested. Different centrifuge times (20, 60, 120, 180 s)
were used and the results show that the maximum absorbance for Hg(II)-Dithizone was obtained in 60 s as the
centrifuge time.

Food Anal. Methods (2014) 7:352359

Interferences
Interfering ions could affect the complex formation of Hg(II)
ions by their interactions with dithizone. The potential interferences of some ions on the preconcentration and determination
of metal ions were examined. To study the effect of interfering
ions, 10 ml of the solution containing 40 g l1 of Hg2+ and the
interfering ions at 100-fold excess were treated at the optimized
conditions followed by the recommended DLLME procedure.
Table 1 shows the tolerance limits of the interfering ions. In the
present study, the tolerance limit of the coexisting ions is
defined as the largest amounts of the coexisting ions that can
change the recovery of the metal ions by 5%.
Statistical and Calibration Parameters
The LOD was 0.15 g l1 based on 3Sb for five replicate
measurements of blank and the enrichment factors was 39.
The linear range was 0.5100 g l1 with a correlation of
determination (R2) of 0.998. The relative standard deviation
for 40 g l1 of Hg(II) was 2.6% (n=5). Analysis on real
Table 1 Effect of interferences ions on the recovery percent of Hg(II)
ions (extraction conditions: 70 l chloroform, 750 l ethanol, pH 1.8,
1.2105 mol l1 of dithizone as a chelating agent, and 1 min centrifugation time)

Salt Effect
The effect of ionic strength of the sample solution on the
extraction of Hg complex was evaluated by addition of
NaNO3 in the range of 00.2 mol l1 into the sample
solution containing 40 g l1 of Hg2+. By addition of salt,
an increase in the extraction efficiency was observed up to
0.15 mol l1 NaNO3 and then it was remained constant.

Fig. 3 The effect of volume of disperser solvent on absorbance of

40 g/l Hg (II). Conditions: 70 l chloroform, different volume of
ethanol, pH 1.8, 1.2105 mol l1 of dithizone as a chelating agent,
and 2 min centrifugation time

Interference

Interference to metal ions ratio (mol/

mol)

Recovery
(%)

Cl
CO32
CH3COO
CN
HCO3
SO42
NO3
SCN
I
H2PO4
Pb2+
Mn2+
Ag+
AuCl4
Bi3+
Fe3+

1,000
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

97.00
91.00
92.20
94.00
93.00
96.30
97.50
100.10
102.30
104.30
96.70
102.05
80.74
77.59
115.29
95.90

Zn2+
Cr2+
Ni2+
Cu2+
Co2+
Cd2+
K+
Na+

100
100
100
100
100
100
1,000
1,000

90.81
97.25
92.47
83.81
98.35
94.06
101.04
97.59

Food Anal. Methods (2014) 7:352359

357

Table 2 Determination and relative recovery of spiked Hg in real samples (extraction conditions: 70 l chloroform, 750 l ethanol, pH 1.8,
1.2105 mol l1 of dithizone as a chelating agent, and 1 min centrifugation time)
Sample
Water
Caspian Sea water
Sefidrood River water
Well water
Sand
Sea sand
River Sefidrood sand
Cigarette
Fish
River fish
Sea fish
Pine leaf

Real sample

Added

Founded

Recovery (%)

10.42 g l1
7.87 g l1
6.41 g l1

10.00 g l1
10.00 g l1
10.00 g l1

20.80 g l1
17.91 g l1
16.52 g l1

101.8
100.2
100.6

17.72 g g1
12.15 g g1
23.80 g g1

10.00 g g1
10.00 g g1
10.00 g g1

27.23 g g1
21.40 g g1
33.40 g g1

95.1
96.6
96.0

1.76 g g1
3.34 g g1
24.04 g g1

10.00 g g1
10.00 g g1
10.00 g g1

11.81 g g1
13.41 g g1
33.91 g g1

100.4
100.5
98.75

samples (River and Sea fish, cigarette, Pine leaf, River and
Sea sand, Sea water, well water and River water) were
performed and satisfactory results were obtained. Because
the amount of Hg in 10 ml of sample solution was measured
after preconcentration in a final volume of 0.1 ml, the
solution was preconcentrated by a factor of 100. The regression equation was A=0.118C+0.652, where A is mean centering of ratio spectra and C is Hg concentration in
micrograms per liter.

Table 2. The recovery of Hg was evaluated using samples

spiked with Hg(II) under the optimum conditions.
According to the results, the spiked Hg can be quantitatively
recovered from all of the samples studied by the proposed
procedure. These results demonstrate the applicability of the
procedure for mercury determination in real samples.

Analysis of Real Samples

A comparison between the presented method and the other

reported preconcentration methods for the Hg extraction and
determination is shown in Table 3. Some of the
preconcentration methods of this table are SDME-ETV-AAS
(Bagheri and Naderi 2009), SDME-high-performance liquid
chromatography-photodiode array detection (Pena-Pereira et
al. 2009), SDME miniaturized spectrophotometer (Yang
et al. 2010), carbon nanotube-based sensor (Safavi et al.

Due to the lack of suitable standard reference materials, the

proposed procedure was applied to determine Hg content of
water samples, cigarette, pine leaf, river and sea fish, and
river and sea sand. The standard addition technique was
used for determination of real samples. The results for water,
sand, cigarette, fish, and pine leaf samples are given in

Comparison of DLLME with the Other Sample

Preparation Techniques

Table 3 The comparison between DLLME and other preconcentration techniques for determination of mercury in environmental samples
Method

LOD

RSD

EF

Linear range (g l1)

References

SDME-ETV-AAS
SDME-HPLC-PAD

0.01
22.8

6.1
11.6

970
3

0.150
80480

Bagheri et al. (2009)

Pena-Pereira et al. (2009)

2
2.7
2.8
4.8

5
6
2.2%
3.6

69

100
150

25
35
39

250
1.030.0

0.53

0.5100

Yang et al. (2010)

Safavi et al. (2010)
Jiang et al. (2006)
Fan (2006)
Pierre (2012)
Brandao et al. (2005)
Tuzen et al. (2009a, b, c, d)
Hong-Jing et al. (2009)
This work

SDME miniaturized spectrophotometer

Carbon nanotube-based sensor
Micro-column-packed GFAAS
Micro-column-packed ICP-OES
ETV-ICP-MS
Cold vapor AAS
SPE-cold vapor AAS
On-line sorption preconcentration CVAFS
DLLME spectrophotometer

0.2
0.64
0.2
0.39
0.12
0.10
0.0025
0.002
0.15

LOD limit of detection (in micrograms per liter), RSD relative standard deviation (in percent), EF enrichment factor

358

2010), micro-column-packed GFAAS (Jiang et al. 2006),

micro-column-packed ICP-OES (Fan 2006), ETV-ICPMS (Pierre et al. 2012). Apparently, this work presented
a low LOD (0.15 g l1) and a short extraction procedure with a simple and inexpensive instrument. These
characteristics are of great interest for the routine laboratories in the trace analysis of Hg ions.

Conclusions
In the present study, a DLLME was developed for extraction
and determination of Hg2+ in real samples. DLLME uses an
extracting solvent with lower toxicity, and it provides high
extraction recovery within a short period of time. The method was successfully applied to determine Hg in environmental samples with high preconcentration factor.
Compared with other methods, such as liquid-phase microextraction, DLLME is fast, simple, inexpensive, and consumes small volumes of organic solvents.

Conflict of Interest Mohadese Hossien poor Zaryabi declares that he

has no conflict of interest. Mahmoud Chamsaz declares that he has no
conflict of interest. Tahereh Heidari declares that he has no conflict of
interest. Mohammad Hossein Arbab Zavar declares that he has no
conflict of interest. Mohammad Behbahani declares that he has no conflict
of interest. Mani Salarian declares that he has no conflict of interest. This
article does not contain any studies with human or animal subjects.

References
Argonne National Laboratory, EVS; U.S. (2005) Department of
Energy, Human Health Fact Sheet
Afkhami A, Bahram M (2006) A novel spectrophotometric method for
the simultaneous kinetic analysis of ternary mixtures by mean
centering of ratio kinetic profiles. Talanta 68:1148
Afkhami A, Bahram M (2004) Mean centering of ratio kinetic profiles
as a novel spectrophotometric method for the simultaneous kinetic analysis of binary mixtures. Anal Chim Acta 526:211
Afkhami A, Bahram M (2005) Mean centering of ratio spectra as a new
spectrophotometric method for the analysis of binary and ternary
mixtures. Talanta 66:712
Afkhami A, Madrakian T, Bahram M (2005) Simultaneous spectrophotometric determination of iodate and bromate in water samples
by the method of mean centering of ratio kinetic profiles. J Hazard
Mater 123:250
Afkhami A, Madrakian T, Bozorgzadeh E, Bahram M (2007) Spectrophotometric determination of beryllium in water samples after
micelle-mediated extraction preconcentration. Talanta 71:1103
Bagheri H, Naderi M (2009) Immersed single-drop microextraction
electrothermal vaporization atomic absorption spectroscopy for
the trace determination of mercury in water samples. J Hazard
Mater 165:353
Bernardo M, Gonalves M, Lapa N, Mendes B (2010) Determination
of alkylphenols ineluates from pyrolysis solid residues using
dispersive liquidliquid microextraction. Chemosphere 79:1026

Food Anal. Methods (2014) 7:352359

Brandao GP, de Campos RC, Luna AS (2005) Determination of mercury
in gasoline by cold vapor atomic absorption spectrometry with direct
reduction in micro emulsion media. Spectrochim Acta B 60:625
Chamsaz M, Arbabzavar MH, Heidari T, Hajnia A, Salehi T (2010)
Spectrophotometric determination of trace amounts of beryllium
in natural water using mean centering of ratio spectra method and
partial least squares regression. Asian J Chem 6:4717
Cheng Q, Dong H (2005) Solvent sublation using dithizone as a ligand
for determination of trace elements in water samples. Microchim
Acta 150:59
Dadfarnia S, Haji Shabani AM (2010) Recent development in liquid
phase microextractionfor determination of trace level concentration of metalsa review. Anal Chim Acta 658:107
Fan J, Qin Y, Ye C, Peng P, Wu C (2008) Preparation of the
diphenylcarbazone functionalized silica gel and its application to
on-line selective solid-phase extraction and determination of mercury by flow-injection spectrophotometry. J Hazard Mater
150:343
Fan ZF (2006) Hg(II)-imprinted thiol-functionalized mesoporous sorbent micro-column preconcentration of trace mercury and determination by inductively coupled plasma optical emission
spectrometry. Talanta 70:1164
Gaona X, Valiente M (2003) Stability study on a West-based methodology to determine organomercury compounds in polluted soil
samples. Anal Chim Acta 480:219
Gao Z, Ma X (2011) Speciation analysis of mercury in water samples
using dispersive liquidliquid microextraction combined with
high-performance liquid chromatography. Anal Chim Acta
702:50
Gharehbaghi M, Shemirani F (2011) Ionic liquid-based dispersive
liquidliquid microextraction and enhanced spectrophotometric
determination of molybdenum(VI) in water and plant leaves samples by FO-LADS. Food and Chem Toxicol 49:423
Hashempur T, Rofouei MK, Khorrami AR (2008) Speciation analysis
of mercury contaminants in water samples by RP-HPLC after
solid phase extraction on modified C18 extraction disks with
1,3-bis(2-cyanobenzene)triazene. Microchem J 89:131
Hong-Jing Z, Wu-Er G, Su-Ping H, Xian-Juan J, Ling-Zhong W
(2009a) Determination of trace inorganic mercury in mineral
water by flow injection on-line sorption preconcentration-cold
vapor atomic fluorescence spectrometry. Chin J Anal Chem
37:1029
Jiang H, Hu B, Jiang Z, Qin Y (2006) Microcolumn packed with YPA4
chelating resin on-line separation/preconcentration combined with
graphite furnace atomic absorption spectrometry using Pd as a
permanent modifier for the determination of trace mercury in
water samples. Talanta 70:7
Kocorova L, Baloghb IS, Skrlkova J, Postac J, Andrucha V (2010) A novel
approach in dispersive liquidliquid microextraction based on the use
of an auxiliary solvent for adjustment of density UVvis spectrophotometric and graphite furnace atomic absorption spectrometric determination of gold based on ion pair formation. Talanta 82:1958
Liang P, Sang H (2008) Determination of trace lead in biological and
water samples with dispersive liquidliquid microextraction
preconcentration. Anal Biochem 380:21
Nabid MR, Sedghi R, Bagheri A, Behbahani M, Taghizadeh M,
Oskooie HA, Heravi MM (2012) Preparation and application of
poly(2-amino thiophenol)/MWCNTs nanocomposite for adsorption and separation of cadmium and lead ions via solid phase
extraction. J Hazard Mater 203:93
Pena-Pereira F, Bendichob ILC, Vidala L, Canals A (2009) Speciation
of mercury by ionic liquid-based single-drop microextraction
combined with high-performance liquid chromatographyphotodiode array detection. Talanta 78:537
Pierre TDS, Rocha RCC, Duyck CB (2013) Determination of Hg in
water associate to crude oil production by electrothermal

Food Anal. Methods (2014) 7:352359

vaporization inductively coupled plasma mass spectrometry.
Microchem J 109:4145
Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani
S (2006) Determination of organic compounds in water using dispersive liquidliquid microextraction. J Chromatography A 1116:1
Roundhill DM (2004) Novel strategies for the removal of toxic metals
from soils and waters. J Chem Educ 81:275
Safavi A, Maleki N, Doroodmand MM (2010) Fabrication of a selective mercury sensor based on the adsorption of cold vapor of
mercury on carbon nanotubes: determination of mercury in industrial wastewater. J Hazard Mater 173:622
Tabrizi AB (2010) Development of a dispersive liquidliquid
microextraction method for iron speciation and determination in
different water samples. J Hazard Mater 183:688
Tuzen M, Karaman I, Citak D, Soylak M (2009a) Mercury(II) and
methyl mercury determinations in water and fish samples by
using solid phase extraction and cold vapour atomic absorption
spectrometry combination. Food and Chem Toxicol 47:1648
Tuzen M, Karaman I, Citak D, Soylak M (2009b) Mercury(II) and
methyl mercury determinations in water and fish samples by
using solid phase extraction and cold vapor atomic absorption
spectrometry combination. Food Chem Toxicol 47:1648
Tuzen M, Karaman I, Citak D, Soylak M (2009c) Mercury(II) and
methyl mercury speciation on streptococcus pyogenes loaded
Dowex Optipore SD-2. J Hazard Mater 169:345
Tuzen M, Sari A, Mendil D, Soylak M (2009d) Biosorptive removal of
mercury(II) from aqueous solution using lichen (Xanthoparmelia

359
conspersa) biomass: kinetic and equilibrium studies. J Hazard
Mater 169:263
Tuzen M, Soylak M (2005) Mercury contamination in mushroom
samples from Tokat, Turkey. Bull Environ Contam Toxicol
74:968
Wen X, Yang Q, Yan Z, Deng Q (2011) Determination of cadmium and
copper in water and food samples by dispersive liquidliquid
microextraction combined with UVvis spectrophotometry.
Microchem J 97:249
Xia L, Hu B, Wu Y (2007) Hollow fiber-based liquidliquidliquid
microextraction combined with high-performance liquid chromatography for the speciation of organomercury. J Chromatogr A
1173:44
Yamini Y, Faraji M (2010) Evolution of dispersive liquidliquid
microextraction method. J Chromatography A 1217:2342
Yang F, Liu R, Tan Z, Wen X, Zheng C (2010) Sensitive determination
of mercury by a miniaturized spectrophotometer after in situ
single-drop microextraction. J Hazard Mater 183:549
Yousefi SR, Shemirani F (2010) Development of a robust ionic liquidbased dispersive liquidliquid microextraction against high concentration of salt for preconcentration of trace metals in saline
aqueous samples: application to the determination of Pb and Cd.
Anal Chim Acta 669:25
Zhoua Q, Zhaob N, Xiec G (2011) Determination of lead in environmental waters with dispersive liquidliquid microextraction
prior to atomic fluorescence spectrometry. J Hazard Mater
189:48